Wales boss Rhian Wilkinson says she feels James leads by example.
“Angharad has been a consistent performer for this team for so many years, which is summed up by the number of appearances she’s made,” she said.
“Her passion and commitment to her country is evident and while she’s not necessarily the most vocal leader, she’s always demanding and offering advice to her teammates when she steps out on the field.
“I love the way she embraces the younger players in the squad with her leadership too, which is important for the future of the team and the direction we’re heading.
“Angharad understands the responsibility that comes with being a captain, both on and off the pitch, and I know this is a proud moment for her and her family.
“I have no doubt she will lead the team as impressively as Sophie Ingle and the former captains of our nation.”
James lands the role as Wales prepare to face Slovakia in the first round of play-offs for the Euro 2025 finals in Switzerland, with the first leg on Friday, 25 October, before the return game at the Cardiff City Stadium on Tuesday, 29 October.
Wales could face the Republic of Ireland, who take on Georgia, in the final of the play-offs if both nations progress.